JP2002105432A - Adhesive, ceramic structural body and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive exhibiting compatibility with a porous ceramic member composed of a porous ceramic excellent enough to bond the porous ceramic members to each other with good bonding strength maintained. SOLUTION: The adhesive is one for bonding a porous ceramic member composed of a porous ceramic, and comprises a linear polymer compound bearing at least a hydroxyl group, an organic binder other than the linear polymer compound, an inorganic binder and an inorganic fiber.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive for bonding a porous ceramic member made of porous ceramic, a ceramic structure used as a particle collecting filter using the adhesive, and the ceramic. The present invention relates to a method for manufacturing a structure.

[0002]

2. Description of the Related Art In recent years, a ceramic structure (ceramic filter) for collecting particulates contained in exhaust gas discharged from an internal combustion engine of a vehicle such as a bus or a truck or a construction machine, and a heat exchanger. Components, high temperature fluids,
Ceramic products made of porous ceramics are manufactured for various applications such as high temperature steam filtration filters.

In manufacturing such a ceramic structure, first, a mixed composition containing a solvent, a binder and the like in addition to the ceramic particles as a raw material is prepared, and extrusion molding or the like is performed using the mixed composition. Then, a ceramic molded body is manufactured. Then, a porous ceramic member is manufactured by subjecting each of the ceramic molded bodies to drying, degreasing, and firing, and then the ceramic block is assembled by laminating the porous ceramic members via an adhesive, thereby obtaining a predetermined ceramic block. The ceramic structure was manufactured by cutting into a shape.

In the above-mentioned ceramic structure manufacturing process, the ceramic block assembled by laminating the porous ceramic members retains its shape, and during the subsequent cutting process and during use as a ceramic filter, the above-mentioned porous ceramic members are formed. The porous ceramic members need to be firmly joined to each other so that they do not fall apart.

Therefore, the present inventors first disclosed in Japanese Unexamined Patent Application Publication No.
As disclosed in Japanese Patent No. 28246, a sealing material (adhesive layer) in which each porous ceramic member contains heat-resistant inorganic fibers, an inorganic binder, an organic binder, inorganic particles, and the like.
We have developed a ceramic structure joined by.

The sealing material (adhesive layer) in the ceramic structure has a certain degree of adhesive strength due to the effect of the entanglement between the inorganic fibers and the organic binder and the inorganic fibers and the inorganic binder contained therein. The thermal conductivity could be ensured.

However, the sealing material (adhesive layer)
Does not have good familiarity with the porous ceramic member, and peeling may occur between the porous ceramic member and the sealing material (adhesive layer), and the adhesive strength is still sufficient. Was not.

[0008]

DISCLOSURE OF THE INVENTION The present invention has been made to solve these problems, and has good compatibility with a porous ceramic member made of porous ceramic, and has a high adhesion between the porous ceramic members. It is an object of the present invention to provide an adhesive that has strong and strong bonding and has excellent thermal conductivity.

Another object of the present invention is to provide a ceramic structure having excellent durability, in which cracks and the like do not occur in the adhesive layer due to vibration, thermal stress, and the like because the adhesive strength of the adhesive layer is large, It is to provide a manufacturing method.

[0010]

The adhesive of the present invention is an adhesive used for bonding a porous ceramic member composed of a porous ceramic, and is a linear adhesive having at least a hydroxyl group. A high molecular compound, an organic binder other than the above-mentioned linear high molecular compound, an inorganic binder, and an inorganic fiber.

The second adhesive of the present invention is an adhesive used for bonding a porous ceramic member composed of a porous ceramic, and is a linear polymer compound having at least a hydroxyl group. It is characterized by containing an organic binder, an inorganic binder, inorganic fibers and inorganic particles other than the linear polymer compound.

In the ceramic structure according to the present invention, a plurality of prismatic porous ceramic members having a large number of through-holes arranged side by side in a longitudinal direction with partition walls are bound together via an adhesive layer to constitute a ceramic block. A ceramic structure configured so that the partition wall separating the through hole functions as a filter for collecting particles, wherein the adhesive layer is formed using the adhesive of the first or second present invention. It is characterized by becoming.

The method for manufacturing a ceramic structure according to the present invention comprises:
The method for producing a ceramic structure, wherein a side surface of a porous ceramic member made of porous ceramic,
A step of applying the adhesive of the first or second aspect of the present invention, repeating a step of laminating another porous ceramic member on the adhesive, and assembling a ceramic block. .

[0014]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The first and second adhesives of the present invention, the ceramic structure of the present invention, and a method of manufacturing the same will be described below.

First, the adhesive of the first invention will be described. The adhesive of the first aspect of the present invention is an adhesive used for bonding a porous ceramic member composed of a porous ceramic, and is a linear polymer compound having at least a hydroxyl group (hereinafter referred to as a hydroxy-containing compound). Compound), an organic binder (hereinafter, also referred to as another organic binder) other than the above-mentioned linear polymer compound, an inorganic binder, and an inorganic fiber.

The adhesive of the first aspect of the present invention having such a composition has good compatibility with a porous ceramic member made of a porous ceramic, and has excellent adhesive strength. The reason for this is not clear, but is considered to be as follows.

The adhesive of the first invention contains two kinds of organic binders, that is, the above-mentioned hydroxy-containing compound and the above-mentioned other organic binder.

Since the above-mentioned hydroxy-containing compound has a hydroxyl group which is a hydrophilic group and is linear,
It is considered that in the adhesive of the first aspect of the present invention, the hydroxy-containing compound and a water molecule in the adhesive form a hydrogen bond. Then, when an adhesive layer is formed on the porous ceramic member made of porous ceramic with the adhesive of the first aspect of the present invention, water molecules in the adhesive layer are present on the surface of the porous ceramic member by capillary action. While being sucked into many open pores, the above-mentioned hydroxy-containing compound which forms a strong hydrogen bond with water molecules is also sucked together with water. As a result, it is considered that a large number of hydroxy-containing compounds (organic binders) are present in the open pores of the porous ceramic member and in the vicinity of the interface.

On the other hand, most of the other organic binders are lipophilic in their properties, and the other organic binders are generally considered to have low affinity for water molecules in the adhesive. Therefore, even if an adhesive layer is formed on the porous ceramic member with the adhesive of the first invention, most of the other organic binder is not absorbed in the open pores of the porous ceramic member. It is considered that they remain in the adhesive layer existing between the porous ceramic members.

Therefore, in the adhesive of the first aspect of the present invention, the hydroxy-containing compound makes the adhesion between the adhesive and the porous ceramic member good, and the other organic binder is an inorganic binder in the adhesive. It is considered that by securing the adhesive force with the adhesive agent of the present invention, the adhesive force of the first adhesive of the present invention as a whole becomes good.

Here, the conventional adhesive also contains an organic binder in its composition, but the organic binder used in such a conventional adhesive is a hydrophilic binder such as polyvinyl alcohol. The compound was not used in combination with another compound. Therefore, the affinity between the adhesive and the porous ceramic member cannot be said to be good, and the porous ceramic member cannot be bonded with high bonding strength.

The hydroxy-containing compound is preferably polyvinyl alcohol. It forms good hydrogen bonds with water molecules and is inexpensive because it is widely used.

The amount of the polyvinyl alcohol to be added is preferably 0.2 to 2.0% by weight in solid content. If the addition amount is less than 0.2% by weight, the familiarity at the interface between the adhesive and the porous ceramic member is reduced.
On the other hand, when the above-mentioned addition amount exceeds 2.0% by weight, the amount of the organic binder to be decomposed and removed in the subsequent degreasing step becomes too large, resulting in a decrease in adhesive strength.

Other examples of the hydroxy-containing compound include, for example, polyglycerin, polyethylene glycol, polypropylene glycol and the like. The addition amount of these compounds is appropriately adjusted in consideration of each molecular weight and its hydrophilicity, etc., but the number of hydroxyl groups in the added compound is approximately the same as the number of hydroxyl groups of the polyvinyl alcohol. It is desirable to adjust as follows.

Examples of the other organic binder include cyclic compounds such as methylcellulose, ethylcellulose and carboxymethylcellulose. The addition amount of the above other organic binder is a solid content,
0.1 to 5.0% by weight is preferable, 0.2 to 1.0% by weight is more preferable, and 0.4 to 0.8% by weight is further preferable. When the content of the other organic binder is less than 0.1% by weight, it is difficult to uniformly disperse the other components in the adhesive layer. When exposed to water, the organic binder is burned off and the adhesive strength is reduced.

Examples of the inorganic binder include silica sol and alumina sol. These may be used alone or in combination of two or more. Among these, silica sol is preferred. The amount of the inorganic binder to be added is preferably 1 to 40% by weight, more preferably 1 to 20% by weight, and still more preferably 5 to 15% by weight in terms of solid content. When the amount of the inorganic binder is less than 1% by weight, the adhesive strength of the adhesive layer is reduced, while when it exceeds 40% by weight, the thermal conductivity is reduced.

As the inorganic fibers, for example, silica
Examples include at least one or more ceramic fibers selected from alumina, mullite, alumina, and silica. Such an inorganic fiber can further improve the adhesive strength of the adhesive layer by being entangled with the organic binder or the inorganic binder.

When the inorganic fiber is a silica-alumina ceramic fiber, its shot content is from 1 to 1
It is preferably 0% by weight, more preferably 1 to 5% by weight, and most preferably 1 to 3% by weight. If the shot content is less than 1% by weight, it is difficult to manufacture. On the other hand, if it exceeds 10% by weight, the surface of the porous ceramic member which is the surface to be bonded may be damaged. The fiber length is preferably 1 to 100 μm, more preferably 1 to 50 μm, and 1 to 20 μm.
Most preferably, it is μm. When the fiber length is less than 1 μm, the property becomes close to that of particles, and the adhesive strength is reduced. On the other hand, if it exceeds 100 μm, it is difficult to uniformly disperse it in the adhesive layer, which also causes a decrease in adhesive strength.

The fiber diameter is preferably 3 to 15 μm. If the fiber diameter is less than 3 μm, the strength is reduced and the fiber is easily cut, resulting in a decrease in adhesive strength. On the other hand, if it exceeds 15 μm, entanglement with an organic binder or an inorganic binder is impaired, which also causes a decrease in adhesive strength. The addition amount of the silica-alumina ceramic fiber is preferably 10 to 70% by weight, more preferably 10 to 40% by weight, in terms of solid content,
20-30% by weight is more preferred. The amount of addition is 10
When the amount is less than the weight%, the adhesive strength of the adhesive layer is reduced.
On the other hand, if it exceeds 70% by weight, the thermal conductivity will be reduced.

In the first adhesive of the present invention, the above-mentioned silicon carbide fibers may be added instead of the above-mentioned inorganic fibers. This is because the thermal conductivity can be maintained at a high level together with the adhesive strength.

This is because the silicon carbide fibers and the inorganic binder in the adhesive layer, and the silicon carbide fibers and the hydroxy-containing compound and the other organic binder are entangled with each other, so that the adhesive strength of the adhesive layer can be improved. It is considered that the silicon carbide fibers are entangled with each other in the adhesive layer and the contact area is increased, and the thermal conductivity is improved as compared with the case where inorganic particles are added.

The fiber length of the silicon carbide fiber is from 20 to 30.
It is preferably 0 μm, and more preferably 50 to 200 μm. When the fiber length is less than 20 μm,
In some cases, the property is close to that of particles, resulting in a decrease in adhesive strength. On the other hand, if it exceeds 300 μm, it is difficult to uniformly disperse the compound in the adhesive layer, which may also cause a decrease in adhesive strength. The fiber diameter is preferably 3 to 15 μm. If the fiber diameter is less than 3 μm, the strength of the silicon carbide fiber is reduced and the silicon carbide fiber is easily cut, which may cause a decrease in the adhesive strength. On the other hand, if it exceeds 15 μm, entanglement with the silica sol is hindered, which may lead to a decrease in adhesive strength, and it is difficult to obtain such a thick silicon carbide fiber itself, leading to a rise in raw material costs.

When the silicon carbide fiber is added to the adhesive layer, the content of the silicon carbide fiber in the adhesive layer is 3
-80% by weight is preferred, 10-70% by weight is more preferred, and 40-60% by weight is even more preferred. When the content of the silicon carbide fiber is less than 3% by weight, the thermal conductivity is reduced. On the other hand, when the content is more than 80% by weight, when the bonding layer 11 is exposed to a high temperature, the bonding strength is lowered. .

As described above, when the adhesive of the first aspect of the present invention forms an adhesive layer on a porous ceramic member, near the interface between the adhesive and the porous ceramic member, water bonds with water molecules. Since the formed linear polymer compound having a hydroxyl group functions as an organic binder, and in other parts, an organic binder other than the above-described linear polymer compound functions, the compatibility between the porous ceramic member and the adhesive layer is improved. And has excellent adhesive strength.

Next, the second adhesive of the present invention will be described. The adhesive of the second aspect of the present invention is an adhesive used for bonding a porous ceramic member composed of a porous ceramic, wherein the linear type high molecular compound having at least a hydroxyl group, the linear type An organic binder, an inorganic binder, an inorganic fiber, and an inorganic particle other than the polymer compound are included.

The adhesive of the second invention contains the hydroxy-containing compound, other organic binder, inorganic binder and inorganic fiber described in the adhesive of the first invention, and further contains inorganic particles. . As described above, by including the above-mentioned inorganic particles, the adhesive of the second present invention has a good affinity between the porous ceramic member and the adhesive layer,
The adhesive strength becomes excellent and the thermal conductivity becomes excellent.

The reason why the porous ceramic member and the adhesive layer are well-adapted and the adhesive strength is excellent has been described in the first adhesive of the present invention, and the description is omitted here. I do. Further, it is considered that the reason why the thermal conductivity is improved by adding the inorganic particles is that the inorganic particles are present on the surface of the inorganic fiber and the surface and the inside of the inorganic binder.

The hydroxy-containing compound, other organic binders, inorganic binders and inorganic fibers are the same as those described in the adhesive of the first aspect of the present invention. Omitted.

The inorganic particles include, for example, at least one or more inorganic powders or whiskers selected from silicon carbide, silicon nitride and boron nitride. The average particle size of the inorganic particles is preferably 0.01 to 100 μm, more preferably 0.1 to 15 μm, and most preferably 0.1 to 10 μm. When the average particle size is less than 0.01 μm, a large amount of inorganic particles is required to secure a certain degree of thermal conductivity, and it is difficult to obtain inorganic particles having such a small particle size, This leads to a rise in manufacturing costs. On the other hand, when the average particle size is 1
If it exceeds 00 μm, on the contrary, the adhesive strength and the thermal conductivity decrease.

When the above-mentioned inorganic particles are silicon carbide, the addition amount thereof is preferably 3 to 80% by weight, more preferably 10 to 60% by weight, and most preferably 20 to 40% by weight in terms of solid content. . If the amount is less than 3% by weight, the thermal conductivity will be reduced, while if it exceeds 80% by weight, the adhesive strength at high temperatures will be reduced.

In the second adhesive of the present invention,
Instead of the inorganic fibers and inorganic particles, the silicon carbide fibers may be used. As described above, the inorganic fiber is
The inorganic particles are added for the purpose of improving the adhesive strength of the adhesive layer, and the inorganic particles are added for the purpose of improving the thermal conductivity of the adhesive layer. However, since the inorganic particles tend to decrease the adhesive strength of the adhesive layer, there is a certain limit in securing both the adhesive strength and the thermal conductivity of the adhesive layer at a high level. However, by using the silicon carbide fiber instead of the inorganic fiber and the inorganic particles,
The adhesive strength and thermal conductivity of the adhesive layer can be secured at a high level.

As described above, the adhesive of the second invention, like the adhesive of the first invention, has good adhesion between the porous ceramic member and the adhesive layer and has excellent adhesive strength. The thermal conductivity is excellent because the inorganic particles in the composition intervene on the surface of the inorganic fiber and the surface and inside of the inorganic binder.

Next, the ceramic structure of the present invention will be described. In the ceramic structure of the present invention, a plurality of prismatic porous ceramic members in which a large number of through holes are juxtaposed in the longitudinal direction with a partition wall therebetween are bound together via an adhesive layer to form a ceramic block. A ceramic structure in which the partition separating the holes is configured to function as a particle-collecting filter, wherein the adhesive layer is formed using the first or second adhesive of the present invention. Features.

FIG. 1 is a perspective view schematically showing an embodiment of the ceramic structure of the present invention, and FIG. 2 schematically shows a porous ceramic member constituting the ceramic structure of the present invention. It is a perspective view.

As shown in FIG. 2, a large number of through holes 21 are formed in the porous ceramic member 20 constituting the ceramic structure, and one end of the porous ceramic member 20 having the through holes 21 is formed. Is a checkerboard filler 2
2 are filled. At another end (not shown), the filler is filled in the through-hole 21 in which one end is not filled with the filler.

Since a large number of through-holes 21 constituting the ceramic member 20 have only one end filled with the filler 22, the exhaust gas flowing from one end of the one through-hole 21 is opened. Always passes through the porous partition wall 23 separating the adjacent through-holes 21 from the other through-holes 21.
Spills through. When the exhaust gas passes through the partition 23, the particulates in the exhaust gas are captured.

FIG. 1 shows a ceramic structure 10 in which a plurality of the porous ceramic members 20 shown in FIG. 2 are bound. In FIG. 1, the through-hole 21 formed in the porous ceramic member 20 is omitted.

In this ceramic structure 10, a plurality of porous ceramic members 20 are bound together via an adhesive layer 11 to form a ceramic block. This adhesive layer 11 includes at least an inorganic binder, an organic binder, and silicon carbide fibers. Including. Further, the entire outer peripheral portion of the ceramic block is coated with the sealing material 12 to form the ceramic structure 10. The shape of the ceramic structure is not particularly limited, and may be a cylinder or a prism, but usually, a cylinder as shown in FIG. 1 is often used.

The material of the porous ceramic member constituting the ceramic structure 10 is not particularly limited, and various ceramics can be used. Among them, heat resistance is high, mechanical properties are excellent, and thermal conductivity is high. Silicon carbide having a high rate is preferable.

The particle size of these ceramics is not particularly limited either, but preferably has a small shrinkage in the subsequent firing step, for example, 100 parts by weight of powder having an average particle size of about 0.3 to 50 μm. It is preferable to use a combination of 5 to 65 parts by weight of a powder having an average particle size of about 0.1 to 1.0 μm. Further, the material constituting the sealing material 12 is not particularly limited, but a material containing a heat-resistant material such as an inorganic fiber and an inorganic binder is preferable. Seal material 1
2 may be made of the same material as the adhesive layer 11.

The material forming the adhesive layer 11 is the above-mentioned first or second adhesive of the present invention, and the description thereof is omitted here.

As described above, the ceramic structure of the present invention uses the first or second adhesive of the present invention for the adhesive layer for binding a plurality of ceramic members. It has good familiarity with the adhesive layer, and is excellent in its adhesive strength or in both its adhesive strength and thermal conductivity. Therefore, the ceramic structure of the present invention does not cause cracks in the adhesive layer due to vibration, pressure of exhaust gas, and the like, and has excellent durability.
In addition to being excellent in durability, deposited particulates can be completely burned off in the regeneration treatment.

Next, a method for manufacturing the ceramic structure of the present invention will be described. The method for manufacturing a ceramic structure according to the present invention is the method for manufacturing a ceramic structure, wherein the adhesive according to the first or second present invention is applied to a side surface of a porous ceramic member made of porous ceramic. And a step of assembling a ceramic block by repeating a step of laminating another porous ceramic member on the adhesive.

In the method for manufacturing a ceramic structure of the present invention, first, a ceramic molded body is manufactured. In this step, after mixing a ceramic powder, a binder, and a dispersion medium solution to prepare a mixed composition for producing a molded body, and extruding the mixed composition, a large number of through holes form partition walls. A columnar ceramic compact formed side by side in the longitudinal direction is produced, and thereafter, the compact is dried to evaporate the dispersion medium liquid, thereby producing a ceramic compact containing ceramic powder and resin. Note that this ceramic molded body may contain a small amount of a dispersion medium liquid.

The appearance of the ceramic molded body is substantially the same as that of the porous ceramic member 20 shown in FIG. 2, and may be an elliptical column or a triangular column. In addition,
In this step, the portion corresponding to the filler 22 is hollow.

The binder is not particularly limited.
For example, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, polyethylene glycol, phenol resin, epoxy resin and the like can be mentioned. Usually, the amount of the binder is preferably about 1 to 10 parts by weight based on 100 parts by weight of the ceramic powder.

The dispersion medium is not particularly restricted but includes, for example, organic solvents such as benzene; alcohols such as methanol, and water. The dispersion medium is mixed in an appropriate amount so that the viscosity of the resin is within a certain range.

Next, as a closing step, a step of closing the above-mentioned through-holes of the produced ceramic molded body in a sealing pattern with a filling paste is performed. At this time, a mask having an opening formed in a sealing pattern is brought into contact with the through hole of the ceramic molded body, and the filling paste is allowed to enter the through hole from the opening of the mask, so that the filling paste is used. Seal the through hole of the part.

The filling paste may be the same as the mixed composition used in the production of the ceramic molded body,
Alternatively, it is preferable that a dispersion medium is further added to the above-mentioned mixed composition.

Next, as a degreasing step, a step of thermally decomposing the resin in the ceramic molded body produced in the above step is performed. In this degreasing step, usually, the ceramic molded body is placed on a degreasing jig, then carried into a degreasing furnace, and heated to 400 to 650 ° C. in an oxygen-containing atmosphere. As a result, the resin component such as the binder volatilizes, and is decomposed and disappears, and almost only the ceramic powder remains.

Next, as a firing step, a step of mounting the degreased ceramic molded body on a firing jig and firing it. In this firing step, the degreased ceramic compact is heated at 2000 to 2200 ° C. in an atmosphere of an inert gas such as nitrogen or argon to sinter the ceramic powder, so that a large number of through-holes extend in the longitudinal direction across the partition walls. To produce columnar ceramic sintered bodies arranged side by side.

In a series of steps from the degreasing step to the firing step, the silicon carbide molded body is placed on a firing jig,
It is preferable to perform the degreasing step and the firing step as they are. The degreasing process and the firing process can be performed efficiently,
Further, it is possible to prevent the ceramic molded body from being damaged when the ceramic molded body is replaced or the like.

As described above, after manufacturing a porous ceramic sintered body in which a large number of through-holes are juxtaposed in the longitudinal direction with the partition wall therebetween, and the partition wall functions as a filter, the porous ceramic sintered body is manufactured. As a binding process of a silicon carbide sintered body,
The above-mentioned adhesive layer is formed on the outer wall portion of the porous ceramic sintered body, and a plurality of the porous ceramic sintered bodies are bound so as to have a predetermined size to produce a ceramic block.

In the step of bundling the porous ceramic members, as shown in FIG. 3, a porous ceramic member placed in an inclined state on a table 60 having a V-shaped cross section. Two side faces 20 facing upward
The first or second adhesive of the present invention is printed on a and 20b using, for example, a brush, a squeegee, a roll, or the like to form an adhesive layer 61 having a predetermined thickness.

Next, another porous ceramic member 20 is laminated on the adhesive layer 61. Then, after forming the adhesive layer 61 on the side surface of such a porous ceramic member 20, the step of laminating another porous ceramic member 20 is repeated to produce a prismatic ceramic block of a predetermined size. I do.

Then, the ceramic block is
After heating and drying and curing at 100 ° C. for 1 hour, the outer peripheral portion is cut in substantially the same manner as the ceramic structure 10 shown in FIG. By forming the sealing material 12 in the portion, the production of the ceramic structure of the present invention is completed.

By performing the steps described above, it is possible to manufacture a ceramic structure having excellent adhesion strength of each ceramic member and high thermal conductivity.

[0068]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 A. Preparation of Adhesive PV-5 (manufactured by Malvan Co., polyvinyl alcohol content 10% by weight) 6.4% by weight, carboxymethylcellulose 0.4% by weight, silica sol (silica content 30% by weight) 24.2% by weight, silica -Alumina ceramic fiber 48.2 wt%, triethanolamine 1.2 wt%, styrene maleic anhydride copolymerized alkyl ester ammonium salt aqueous solution (ELF Atochem No.
0.1 wt% of SMA (manufactured by rth America Inc.) and 19.5 wt% of water were mixed and kneaded to prepare an adhesive A for bonding a porous ceramic member.

B. Manufacture of porous ceramic member 70 parts by weight of α-type silicon carbide powder having an average particle diameter of 10 μm, 30 parts by weight of β-type silicon carbide powder having an average particle diameter of 0.7 μm, 5 parts by weight of methylcellulose, 4 parts by weight of dispersant, and 20 parts by weight of water The components were mixed and uniformly mixed to prepare a mixed composition of raw materials. This mixed composition was charged into an extruder, and a honeycomb-shaped formed body was produced at an extrusion speed of 2 cm / min. This formed form is almost the same as the porous ceramic member 20 shown in FIG.
mm × 300 mm, the average pore diameter was 1 to 40 μm, the number of through holes was 31 / cm ² , and the thickness of the partition wall was 0.35 mm.

Using a filler paste of the same component as that of the above-mentioned mixed composition, a filler is filled in a predetermined portion of the through hole of the silicon carbide sintered body, and then degreased at 450 ° C. Further, by heating and firing at 2200 ° C., a porous silicon carbide member having a size of 33 mm × 33 mm × 300 mm was manufactured.

Next, the adhesive A prepared in the above A was attached to one outer peripheral surface of the porous silicon carbide member manufactured in the above B,
An adhesive layer was formed. Then, another porous silicon carbide member is placed on this adhesive layer, dried and cured at 100 ° C. for one hour, and a porous silicon carbide member in which three porous silicon carbide members are continuously bonded is formed. A conjugate was made.

Example 2 A. Preparation of Adhesive PV-5 (Malvan Co., polyvinyl alcohol content 10% by weight) 5.08% by weight, carboxymethyl cellulose 0.32% by weight, silica sol (silica content 30% by weight) 18.93% by weight, silica 37.86% by weight of alumina ceramic fiber, 24.57% by weight of silicon carbide powder (GC-15, manufactured by Yakushima Denko Co., Ltd.), 0.97% by weight of triethanolamine, styrene maleic anhydride copolymerized alkyl ester ammonium salt aqueous solution ( ELF A
tochem North America Inc
SMA) 0.08% by weight and 12.19% by weight of water are mixed and kneaded, and an adhesive B for bonding a porous ceramic member is used.
Was prepared.

B. Manufacture of porous ceramic member 70 parts by weight of α-type silicon carbide powder having an average particle diameter of 10 μm, 30 parts by weight of β-type silicon carbide powder having an average particle diameter of 0.7 μm, 5 parts by weight of methylcellulose, 4 parts by weight of dispersant, and 20 parts by weight of water The components were mixed and uniformly mixed to prepare a mixed composition of raw materials. This mixed composition was charged into an extruder, and a honeycomb-shaped formed body was produced at an extrusion speed of 2 cm / min. This formed form is almost the same as the porous ceramic member 20 shown in FIG.
mm × 300 mm, the average pore diameter was 1 to 40 μm, the number of through holes was 31 / cm ² , and the thickness of the partition wall was 0.35 mm.

Using a filler paste of the same component as the above-mentioned mixed composition, a filler is filled in a predetermined portion of the through hole of the silicon carbide sintered body, and then degreased at 450 ° C. Further, by heating and firing at 2200 ° C., a porous silicon carbide member having a size of 33 mm × 33 mm × 300 mm was manufactured.

Next, the adhesive B prepared in the above A was attached to one outer peripheral surface of the porous silicon carbide member produced in the above B,
An adhesive layer was formed. Then, another porous silicon carbide member is placed on this adhesive layer, dried and cured at 100 ° C. for one hour, and a porous silicon carbide member in which three porous silicon carbide members are continuously bonded is formed. A conjugate was made.

Comparative Example 1 As an organic binder, PV-5 (manufactured by Malvan Co., polyvinyl alcohol content: 10% by weight) 11.73% by weight,
15. 59.13% by weight of ceramic fiber made of alumina silica as inorganic fiber, and silica sol (content of SiO ₂ in sol: 30% by weight) as inorganic binder.
A bonded body of a porous silicon carbide member was produced in the same manner as in Example 1, except that an adhesive for a porous ceramic member was prepared using 19% by weight and 12.95% by weight of water.

Comparative Example 2 Carboxymethylcellulose was used as an organic binder.
5% by weight, 23.3% by weight of silica-alumina ceramic fiber as inorganic fiber, 7% by weight of silica sol (SiO ₂ content in sol: 30% by weight) as inorganic binder, silicon carbide powder having an average particle diameter of 0.3 μm A bonded body of a porous silicon carbide member was produced in the same manner as in Example 1, except that 30.2% by weight and 39% by weight of water were prepared to prepare an adhesive for a porous ceramic member.

The performance evaluation of the composite of the porous silicon carbide members manufactured in Examples 1 and 2 and Comparative Examples 1 and 2 was measured by the following method.

[0080]Evaluation method  (1) Measurement of adhesive strength As shown in FIG. 4, two prismatic members are arranged on a table.
Subsequently, the above-mentioned combined body is connected to a porous silicon carbide member at both ends.
Is placed on the above prismatic member,
Load was applied to the porous silicon carbide member, and the adhesive layer peeled off
The load at the time was measured, and its bending strength was determined. Also, actually
Is expected to be rapidly heated and cooled from room temperature to about 900 ° C.
Heat cycle test from room temperature to 900 ° C
(100 times) and the same evaluation
went. The results are shown in Table 1 below.

(2) Measurement of Thermal Conductivity As shown in FIG. 5, after the above-mentioned combined bodies are placed one on top of the other, the outer periphery thereof is surrounded by a heat insulating material 30 and placed on a heater 31 at 600 ° C. by heating for 30 minutes, to measure the temperature difference between the temperatures T ₁ and the temperature T ₂ of the lower portion of the upper.
Table 1 shows the results.

[0082]

[Table 1]

As is clear from the results shown in Table 1, the typical bonding strength of the bonding layer of the bonded body of the porous silicon carbide members according to Examples 1 and 2 is 0.7 to 0.8 MPa, The temperature difference between its upper and lower ends is 150-170 ° C,
The typical bonding strength of the bonding layer of the bonded body of the porous silicon carbide members according to Comparative Examples 1 and 2 is 0.1 to 0.2 MPa, and the temperature difference is 250 to 260 ° C. It was inferior to the combination of the porous silicon carbide members. In this example and the comparative example, the adhesive strength and the thermal conductivity were measured using three porous silicon carbide members that were continuously bonded. , To join a number of porous silicon carbide members,
The difference between the values of the adhesive strength and the thermal conductivity becomes even more pronounced.

[0084]

The adhesive according to the first aspect of the present invention is as described above, so that the adhesion between the porous ceramic member made of porous ceramic and the adhesive layer is good, and the adhesive strength between the porous ceramic members is high. And can be firmly joined.

Since the adhesive of the second aspect of the present invention is as described above, the adhesive between the porous ceramic member made of porous ceramic and the adhesive layer is good, and the adhesive strength between the porous ceramic members is high. , And the thermal conductivity of the adhesive layer can be maintained at a high level.

As described above, the ceramic structure of the present invention is formed by using the first or second adhesive of the present invention, so that the porous ceramic member and the adhesive layer are well adapted and the adhesive strength is high. And it is excellent in thermal conductivity.

The method for manufacturing a ceramic structure according to the present invention comprises:
As described above, the familiarity between the porous ceramic member and the adhesive layer is good, and a ceramic structure excellent in adhesive strength and thermal conductivity can be manufactured.

[Brief description of the drawings]

FIG. 1 is a perspective view schematically showing one embodiment of a ceramic structure of the present invention.

FIG. 2 is a perspective view schematically showing a porous ceramic member constituting the ceramic structure of the present invention.

FIG. 3 is an explanatory view schematically showing how a ceramic block is manufactured.

FIG. 4 is an explanatory view of a measurement test of adhesive strength.

FIG. 5 is an explanatory diagram of a measurement test of thermal conductivity.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 Ceramic structure 11 Adhesive layer 12 Sealing material 20 Porous ceramic member 21 Through-hole 22 Filler 23 Partition wall 30 Heat insulating material 31 Heater

Claims (6)

[Claims] 1. An adhesive used for joining a porous ceramic member composed of a porous ceramic, wherein the adhesive is a linear polymer compound having at least a hydroxyl group, and other than the linear polymer compound. An adhesive comprising an organic binder, an inorganic binder and an inorganic fiber. 2. An adhesive used for joining a porous ceramic member composed of a porous ceramic, wherein the adhesive is a linear polymer compound having at least a hydroxyl group, and other than the linear polymer compound. An adhesive comprising an organic binder, an inorganic binder, inorganic fibers and inorganic particles. 3. The adhesive according to claim 1, wherein the linear polymer compound having at least a hydroxyl group is polyvinyl alcohol. 4. The amount of polyvinyl alcohol to be added is 0.1.
The adhesive according to claim 3, wherein the amount is 2 to 2.0% by weight. 5. A ceramic block comprising a plurality of prismatic porous ceramic members having a large number of through-holes juxtaposed in the longitudinal direction with a partition wall interposed therebetween through an adhesive layer.
A partition wall separating the through-hole is a ceramic structure configured to function as a particle collection filter, and the adhesive layer is formed using the adhesive according to any one of claims 1 to 4. A ceramic structure characterized by comprising: 6. A ceramic block comprising a plurality of prismatic porous ceramic members having a large number of through-holes juxtaposed in the longitudinal direction with a partition wall interposed therebetween through an adhesive layer.
2. A method for manufacturing a ceramic structure, wherein a partition partitioning the through hole functions as a filter for collecting particles, wherein a side surface of the porous ceramic member is provided.
5. A ceramic structure comprising a step of applying the adhesive described in any one of (1) to (4) and repeating a step of laminating another porous ceramic member on the adhesive to assemble a ceramic block. Manufacturing method.